1, 4-diaminoanthraquinone compounds containing a cyano group in the 2-position



Patented June 6, 1950 UNITED STATES PATENT OFFICE 1,4-DIAMINOANTHRAQUINONE COMPOUNDS CONTAINING A CYANO GROUP IN THE 2- POSITION Joseph B. Dickey and Anthony Loria, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application November 1, 1947, Serial No. 783,623

6 Claims. (Cl. 260-380) wherein Q stands for a group such as the methyl group, the ethyl group, the propyl group, the isopropyl group, the n-butyl group, the p-hydroxyethyl group, the fi -dihydroxypropyl group, the phenyl group, or the p-tolyl group and Q1 stands for a group such as the methyl group, the ethyl group, the p-hydroxyethylgroup, the 5, dihydroxypropyl group, the phenyl group, or the p-tolyl group are known, and all or practically all of the possible compounds having the above formula have been tested as dyes for cellulose acetate textile materials. However, while certain of these compounds were regarded as good dyes for cellulose acetate textile materials when initially tested for this purpose, they are not as highly regarded as they once were. Specifically, when employed for the dyeing of cellulose acetate textile materials, these compounds leave much to be desired with respect to one or more of the dyeing properties enumerated hereinafter, i. e., the fastness of the dyed material to light, the fastness of the dyed material to gas and the affinity of the dye for the textile material. Accordingly, much time and efiort has been directed to the preparation of dyestuffs which will really satisfactorily color cellulose carboxylic ester fibers of the above character.

It is an object of our invention to provide new anthraquinone compounds which possess good affinity for cellulose carboxylic ester textile materials, in which ester the'acid radical contains from 2 to 4 carbon atoms, and which yield dyeings on these textile materials which have good fastness to light and: gas, A further object is to provide a satisfactory process for preparing our new anthraquinone compounds. Another object is to provide new anthraquinone compounds which are superior to the known anthraquinone compounds mentioned hereinbefore for the dyeing of cellulose acetate textile materials.

A- still further object is to provide dyed cellulose carboxylic ester textile materials of the character defined herein, which possess good fastness to light and gas. Other objects will appear hereinafter.

The new'compounds of our invention by means of which the above objects are accomplished or made possible have the general formula:

wherein R stands for a hydrogen atom, an alkyl six, inclusive, carbon atoms, Y represents an OR1(OR1)n-OH group and an (OR2) m-OR3 group wherein R1 and R2 each represent an ethylene group, a propylene group, or a trimethylene group, R3 represents a methyl group or an ethyl group, n stands for a whole positive integer of from one to three, inclusive, m stands for a whole positive integer of from two to three, inclusive, and wherein n is three R1 is ethylene, and X represents a hydrogen atom, a halogen atom, a methyl group, an ethyl group, a hydroxy group, or an acetamino group.

The range of colors of cellulose'carboxylicester textiles dyed with the anthraquinone compounds of our invention extends from bluish-green to greenish-blue shades. Silk, wool, and nylon textile materials may also be colored with the dyes of our invention.

The anthraquinone compounds of our inven tion are prepared by reacting an anthraquinone compound having the formula:

wherein R, X, and Y have the meanings previously assigned to them with cuprous cyanide in 3 4 the presence of quinoline. The reaction may be water, and dried. It colors cellulose acetate carried tout by heating. under reflux at oatmosgreenish-blue shades having excellent lightand pheric pressure .or lay-heating in asealed'autoas-fastness properties.

clave. After the reaction mixture resulting from g g g ..1 mino-g cyano 4-( fl..h dr q;y heating together the aforesaid materials has: 5 i; p ethoacy ,B ethomy-[i-ethozcyethoaryphenyl) cooled, the desired anthraquinonet-dye iserecove a noant mqui ne ered therefrom in any suitable manner. In one- 5.8 gra of l- D-B- yembodiment of our invention we pour the reacdrOXy fl BthOXY fl Y-B- Y Y- tion' mixture into dilute hydrochloricacid, and phenyl) aminoanthmquinoner 1 gram of after a short digestion at'about 70 C. to dissolve Cupmus cyanide, 9 quinolme f the copper Salts whichoarepresem-ywe, cool t heatediunder reflux-with stirringfor approxireaction mixture and recover the-precipitated dye mate1y one 110111; The reaction 2 by filtration. In another embodiment of the lowed 001 to t0'50 C. at which po1 nt 1t 15 inventionwemter the bbflmgquinohhe,Solution poured into an excess of dilute hydrochlonc acid. to removethecopper salts and the resulting clear Tlfle resulting r y 1S? at d- C- r 30 solution is cooled to crystallize thedye which is 5 'm and when (3091 the (issued f compound then recovered by filtration. The resulting filf by fill/mum Washed Wlth Water, and trate may be concentrated under reduced pres- The dye colors Fellulose acetate deep sure in order to obtain from a-nsecond crystallizagreemshblue Shades havmg Very good fastness tion an additional yield of dye compound. The Properties- I first procedure for recovering the dye from the 30 Example 3.--1-amino-2-cyano-4-(p-y-hydromyreaction mixture ordinarily gives higher yields. 'y-p1"opozvy-'y-propoxypropomyphenyl) amino- The following examples illustrate the anthraanthraquinone IP'H:

fig -oontoraont-oonicniom -ooniorucnkon quinone compounds of our-"invention and the 5.8 grams of 1-amino-2-bromo-4-(p-y-hymanner in WhlChTthey are prepared; droxy-v-propoxy--y-propoxypropoxyphenyl) am- Example inoanthraquinone, 1 gram of cuprous cyanide, droxy 5 ethowwaethommethoxy-phenyz) and cc. of quinoline are heated under reflux aminoanthmqm-none 45'f0r three to four hours. The boiling solution is filteredhot and allowed to cool. The precipitate wh-ich.forms -is recovered by. filtration andthe filtrate is concentrated by distillation under reduced pressuretoa point where oncoolinga 'further. crop of crystals. forms. These crystals are .collectedand added to. the. first yield and the N O-OOHiCHi-OCHaGHfOCHiCHzOH total-is washed withwater anddried. The re.- sulting. dye compound colors cellulose acetate 6.5 grams of 1-arn1no-2ebromoe4e(para B-hyfast greenishmlueyshadesr droxy- B eth'oxyl-fl-ethoxyethoxyphenyl) .-aminoanthraquinone', 1.2 grams of cuprous; cyanide and Example 4.-1-methylamino-2-cyano-4-(para-v- 50 grams-of dry quinoline are heated'under'refiux hZ/TOIEZI-'y -ZJTOZJOIEy-7-PTOPOfiCZIIJTOPOJig19h6ni/Z)- with" stirring for approximately one hour; The aminoanthmquinone i 0. N-CH;

reaction mixture is allowed to cool to 40 C. to 6:0:gramsof 1-methylamino-2-bromo-4-(para- 50 C. whereupon it is pouredwith stirring into v-hydroxy-'y-propoxyevepropoxypropoxyphenyl1 230 cc. of 9%.hydr0ch10ric acid; The suspension aminoanthraquinone, lgram of cuprous cyanide, resulting is heated at..70 C. for 30 minutes and and-5O cc. of.quinolineare-reacted together and then allowedtocool'to room temperature. The worked up in accordance-with the procedure dedesired dye compound which precipitates is 001- scribed in Exampleli The:resulting dye comle'cted bysuction filtration, washed free of acid pound colors cellulose. acetate bluish-green with dilute sodiumcarbonateand :i then. cold shades. I v

Example 5.1-p-methoxyethylamino-z-cwm '4' (p p hydroxy-p-ethoay-p-ethoxyethomyphenyl) aminoanthraqainone g gooomonro omom-o CHzCHi-OH 6.0 grams of l-p-methoxyethylamino-z-bromo- 4 (pp hydroxy. p ethoxy-p-ethoxyethoxyphenyl) aminoanthraquinone, 1 gram of cuprous cyanide, and 50 cc. of quinoline are reacted'together and worked up in accordance with the procedure described in Example 1. The resulting. dye compound colors cellulose acetate bluishgreen shades.

Example 6.1 B- fihydromyethomy) ethylamino- Z-cyano-4- (ortho-methyl-para 5 ethowy-flethoazyethoxyphenyl) aminoanthra qainone g? omonro omom-o 011,011;

6.4 grams of 1 fl (p-hydroxy-ethoxymthylamino-2 bromo 4 (ortho methyl para p ethoxy p ethoxyethoxyphenyl) aminoanthraquinone, 1 gram of-cuprous cyanide, and ,50 cc. of quinoline are reacted together and worked up in accordance with the procedure described in Example 3. The resulting dye compound colors cellulose acetate bluish-green shades.

Example 7.1-p-hydroxyethylamino-2-cyano-4- (p-fl-hydroxy-fl-ethomys-ethoa;y I8 ethomyethoxyphenyl) aminoanthraqainone H O N-CHzCHa-OH 6.3 grams of 1-B-hydroxyethylamino-2-bromo- 4-(p-fl-hydroxyfl-ethoxy-fl-ethoxy p ethoxyethoxyphenyl) aminoanthraguinone, 1 gram of cuprous cyanide, and 50 cc. of quinolinefare reacted together and worked up in accordance with the procedure described in Example 1. The resulting dye compound colors cellulose acetate bluish-green shades.

Example 8.1-amino-2-cyano-4- (p-p-methoazy- B ethoxy B ethoxyethoxyphenyl) aminoanthraqainone 0 NH: C

5.5 grams or 1-am1no-2-bromo-4-(p-p-methoXy-fl-ethoxy p ethoxyethoxyphenyl) aminoanthraquinone, 1 gram of .cuprous cyanide, and 50 cc. of quinoline are reacted together and worked up in accordance with the procedure described in Example 1. The resulting dye compound colors cellulose acetate greenish-blue shades.

Example 9.1 butg lamino-2-cyano-4- (p-p-hydroxy p ethozcy p ethoa'yethoaz pheayl)v aminoanthraquinone H O N-CHaCHICHzCH:

0 u -0011,0nro mcnl-opmom-on.

6.0- grams of 1-butylamino-2- bromo 4 (p-phydroxy-fi-ethoxy-B-ethoxyethoxyphenyl) aminoanthraquinone, 1 gram of cuprous cyanide, and 50 cc. of quinoline are reacted together and worked up in accordance with the procedure described in Example 1. The resultingdyecompound colors. cellulose. acetate bluish-green shades.

Example 10.--1-amino-2-cyano-4- (para p hydrvwzl J ethomy thowph nyl) laminoanthraquinone 5.0 grams of 1-amino-2-bromo-4-(para-fi-hydroxy fi-ethoxyethoxyphenyl) aminoanthraquinone, 1- gram of cuprous'cyanide, and 50 cc. of

quinoline are heated under reflux for three to four hours. The boiling solution is filtered hot and allowed to cool. The blue dye crystals which separate are recovered by filtration, and the filtrate is concentrated under reduced pressure to a point where on cooling a further crop of crystals forms. These crystals are collected and added to the first yield, and the total is washed with water and dried. The dye compound thus obtained colors cellulose acetate greenish-blue shades.

7 Ezzample 1 1 .1 ;=te1:tiaryebwtylamino+2ecyano el- (OItlLOrMZCfitGMiILQflGYIGeFJY hydromy- 7- propoxypropoxyphenyl). aminoanthraquinone OCHaCHzCHrO-CHzCHaCHrOH N-CO-CH: H

Example .12;-1 i- 5, dihydroxypropyZamino-Z- cyano- 4 (p-fi 'hyd10mg ,3--- propozcypropoxyphenyl) ammoanthmquz'none to a a 6.0 grams of 1-,c,'y-dihydroxypropylamino-Z- bromo-4 (p 3 hydroxy-p-propoxypropoxyphenyl') aminoanthraquinone; 1 gram of cuprous iodide, and-.501ccrotiquinoline are reacted together and worked; up i inaaccordance with the procedure described in Example 3. The resulting dye compound formulated above colors cellulose acetate bluish-green shades.

Example 13.--1-amino-2-cyano-4- (p ,8 methox' 13 ethoxyethoxyphenyl) aminoanthraquinon'e O CHaCH--O CHzCH-OH CH CH3 511 grams of. 1+aminm2-bromo-4-(p-B-methcxy ,6 ethoxyethoxyphenyl aminoanthraquinone;-1 gram of cuprous cyanide-and 50 grams of quinoline are;heated-under reflux with stirring for=approximatelyone hour.- Thereaction mixture is then cooled to 40 C. to 50 C. whereupon it is poured with stirring into 230 cc. of 9% hydrochloric acid. The suspension resulting is. heated at 70 C. for 30 minutes and then cooled to room temperature. A good yield of the desired dye compound precipitates and is collected by filtration, washed free of acid with dilute sodium carbonate and then cold Water, and dried. It colors cellulose acetate greenish-blue shades of excellent lightand gas-fastness.

6.6 grams of 1-fi-ethoxyethylamino-2-bromo- 4 (o chloro p -p-methoxy-p-ethoxy-c-ethoxyethoxyphenyl) aminoanthraquinone, 1. gram of cuprous cyanide, and 50 cc. of quinoline are reacted together and worked up in accordance with the procedure of Example 1. The dyecompound obtained, colors cellulose acetate. bluish-green shades.

Example. Y 1551 hudromu- .vepropoxypmpylamino, 2;.-', cznmaflao-hydromuepep-ethoxy-cethomu-fl ethoxyetltomyphenyl) aminoanthm quinone 7.0 grams of 1w-hydroxy-v-propoxypropylamino 2 bromo 4"- ('o-hydroxy -p p-ethoxy-flethoxy-c-ethoxyethoxyphenyl) aminoanthraquinone, 1 gram of cuprous cyanide, and 50 cc. of qu'inoline arereactediegether a-nd Workedup, in accordance with; the-procedure described in -Example -1. The. resulting idyezacompound; colors cellulose acetate greenish-blue shades.

Example 16.-1-y-methomypropylamino-2-cyano- 4 (o ethyl -10-c-hydroa:y-cwillow-d emonethoacyphenyl) aminoanthraquinone.

6.4 grams of 1-Y-methoxypropylamin0-2- bromo 4 (o ethyl -p-p-hydr0xy -fl-ethoxy-fiethoxyethoxyphenyll aminoanthraquinone, 1 gram of cuprous cyanide, and 50';cc.-of quinoline are reacted together and worked up in accordance with the procedure described in ,Example 1. The-r sllltinadye,compoundcolors celluloseaca tatebluish-green-shades,

In: order that. thespreparation-ot the com,- pounds. of our invention maybe.entirelyclear the: preparation 1 of various intermediate. comp ounds used. intheir manufacture is described hereinafter.

The preparation of the lrbdiamino-Z-bromoa-nthraquinone compounds; having the; general formula:

wherein R, X, and Y have the meaning previously assigned is; described a in the copending U. S. patent, applicatiomserial Number 731,424 of J. B. Dickey, A... Loria,, andE. B.. Towne, now Patent No. 2,487,045., Anthraquinone compounds of the. generalformula:

wherein R has the meaning previously assigned to it are reacted with an amine having the formula:

wherein X and Y have the meanings previously given to them. The reaction is ordinarily carried out in the presence of an inert organic diluent such as n-amyl alcohol, n-butyl alcohol or isopropyl alcohol and a copper salt catalyst such as finely powdered cupric sulfate or cupric acetate. The use of n-amyl alcohol has been found to be advantageous. Ordinarily an acid binding agent such as potassium acetate, sodium acetate, ammonium acetate, sodium bicarbonate, potassium bicarbonate, sodium carbonate, or potassium carbonate, for example, is also present.

The following examples illustrate the manner of preparation of these compounds.

Example A.-1-amino-2-bromo-4-(p-p-hydroryp ethozry p ethozcy-p-ethoxyethoxyphenyl) aminoanthraquinone 38 grams of 1-amino-2,4-dibromoanthraquinone, 28.5 grams of p-B-hydroxy-fi-ethoxy-pethoxy-p-ethoxyethoxyaniline, 10 grams of potassium acetate and 1 gram of finely powdered copper sulfate (CuSO4-5I-I2O) are heated together under refiux with stirring, in 150 cc. of n-amyl alcohol for seven hours. The desired compound is isolated and purified by either of the followin methods: 7

METHOD I The reaction mixture is taken to dryness in vacuoon a steam bath. 250 grams of toluene are added, the reaction mixture heated to boiling, filtered hot, and the insoluble material washed with 50 grams of boiling toluene. The filtrate is cooled to 15 C. and 80 grams of petroleum ether are added over a five minute period with good stirring, cooling is continued until the temperature is -5 0., and after one hour the compound is solid. The procedure may be repeated without decreasing the yield to any extent and should be repeated if the product is gummy at this point. If the precipitation procedure is to be repeated, the compound should be first heated to 50 C. for a few minutes to remove any residual petroleum ether that will hinder the solubility of the compound in toluene. The compound is recovered by filtration, washed with 50 grams of petroleum ether and dried at 40-50 0.

METHOD II Example B.1 amino 2 bromo 4 (para-B- hydrory p ethozcy ,9 ethoxyethomyphenyl) aminoanthmquinone 38.1 grams of 1-amino-2,4-dibromoanthra- "quinone, 30.6 grams of para-p-hydroxy-p-ethoxyp-ethoxyethoxyaniline, grams of potassium acetate, and 1 gram of finely divided copper sulfate (CuSO4-5H2O) are heated together under reiiux with stirring in 150 cc. of n-amyl alcohol for seven hours. The resulting compound is isolated and purified by Method I or Method II.

Example C.-1-methylamino 2 bromo-4- (p-Y- hydromy 'y propomy-y-propowypropomyphenyl) aminoanthraquinone 39.5 grams of 1-methylamino-2.4-dibromoanthraquinone, 28.3 grams of p-y-hydroxy-"ypropoxy-v-propoxypropoxyaniline, 10 grams of potassium acetate, and 1 gram of finely powdered copper sulfate are heated together under reflux with stirring in 150 cc. of n-amyl alcohol for seven hours. The resulting compound is isolated and purified according to the procedure of Method I 01' Method II.

Equivalent amounts of any of the anthraquinone compounds having the formula:

wherein R has the meaning previously assigned toit may be substituted for the l-amino-ZA- dibromoanthraquinone of Example A. And equivalent amounts of any of the aniline derivatives having the formula:

The preparation of aniline derivatives having the formula:

wherein X and Y have the meanings previously assigned to themhas been described before, for example, in U. S. Patent 2,391,011, issued December 18, 1945, to J. B. Dickey and J. R. Byers, Jr. A compound having the formula:

0 02114-0 0231-0 2114-0 C2H4-OHJ (wherein X has the meaning previously assigned to it) which is not within the scope of this reference is prepared by reacting equimolar portions of sodium and tetraethylene glycol and then condensing the sodium alcoholate formed with the desired chloronitrobenzene compound. The con- .densation is advantageously carried out at to C. for about twenty hours. The nitro compound formed is then reduced with hydrogen in the presence of a nickel catalyst, especially of the Raney type, in methanol, at 80 to 100 C. in an autoclave under a hydrogen pressure of 400 to 1800 pounds per square inch.

Compounds having the formula:

H O N-R wherein R has the meaning previously assigned emcee ii to it can be prepared by brominating a compound having the formula:

Preparation of 1-methg Zamino-2,4-dibrmoanthraquz'none 23.7 grams of 1-methylaminoanthraquinone and 2-1.6 grams of potassium acetate are placed in 260 cc. of glacial acetic acid and the reaction mixture resulting is heated, with stirring, to 60-65 C. 35.5 grams of bromine in cc. of glacial acetic acid are added slowly over a period of 1-2 hours while maintaining a reaction temperature of 60 C.-.-65 C. The reaction mixture is maintained at 60 C.65 C. for 3-4 hours and then cooled and filtered. 1 -methylan i ino-2,4-dibromoanthraquinone melting at162? C.-16 3," C. is obtained upon crystallizing the product recovered on th filter from, lacial acetic acid. A o yield of the product in less pure form can be btai d. by p ur n the r acti n. mix ure n 3 liters of cold water and filtering. By the use of I y r r eiby am noan h quinon instead of l-ethylaminoanthraquinone in the foregoing example, 1-p-hydroxyethylamino-2,4-dibromoanthraquinone melting at 226 C.229 C. is obtained.

The cellulose carboxylic esters which may be dyed or colored with the anthraquinone compounds of our invention include hydrolyzed as well as unhydrolyze'd' cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetatepropionate and cellulose aeetate-butyrate. While our new anthraquinone compounds have been illustrated more particularly in connection with the coloration of cellulose acetate, a material to which they are especially adapted, it will be understood that they can be used fox-the coloration of the other aforesaid cellulose carboxylic esters. Our new compounds are also useful for the coloration of cellulose ester and cellulose ether lacquers as well as lacquers made from polyvinyl compounds and. they also possess some utility for the coloration of nylon and textile materials prepared therefrom.

The anthraquinone dyes of our invention can be applied to the coloration of fabrics made of or containing a cellulose carboxylic ester,- such as cellulose acetate rayon, by the known dyeing or printing methods, In accordance with the known dispersion method of dyeing, the anthraquinone dyes are first ground to a fine powder, intimately mixed with a suitable dispersing or solubilizing agent, following which the resulting mixture is added towater or a dilute solution of soap in water to form-an aqueous dye bath. The textile materials are then immersed in such a dye bath in accordance with known procedures. Suitable dispersing or solubilizing agents include soap, sulforicinoleic acid, the-alkali metal salts of sulforicinoleic acid, sulfonated oleic, stearic or palmitic acid or salts thereof, such as the sodium or ammonium'salts. For printing, *our-new'dyes 12 are advantageously ground with asuitable dispersing agent, such as *a'sodium lignin'sulfonate and the resulting printing mixture is then appliedto the textile-materials, in accordance with known printing methods.

In accordance with the recommendations of Chemical Abstracts, the term propylene is intended to mean "the "group having =the'following formula:

oHl[o'H- H; and the term trime-thylene is intended to mean the group havingfollowing formula:

CH2'-CH2'-GH2' We claim:

1. The anthraquinone compounds having the formula:

wherein, R- represents a.- member :seleet'ed firom the group consistingofi a hydrogen atom, :an alkyl .grouplhaving-one tofiour, inclusiive carbon atoms, a. hydroxyalkylgroup-having two; tothree, inelusive, carbon atomaar .alkoXyalkyl/gmup haw ingithree. tofour, inclusiye,:'carbon atoms, anda r m e-g w; o s st ne Of a methy group enda e hyl, r uper; st ndsjfor air/h l pos iv integer of from one toth gee, inclusive, mstands for a whole positive integer of from two to three, inclusive, and wherinwhenn is three, R1 is ethylene, and X represents a member selected from the group consisting. "of a hydrogen atom, a halogen atom, amethylf'group, an ethyl group, a hydroxy group,andanja'cetamino group.

2. The anthraquinone compou d having the formula:

wherein nrepresents a-K whole; positive integer of from; one ;to c three; inclusive.

3. The anthraquinonei compounds. having the formula;

14 wherein m represents a whole positive integer of 4. The anthraquinone compound having the from two to three, inclusive, and R3 stands for a. formula:

(H) NH 0 g -o-omcm-ooH,0H,-0-oH,0H0H member selected from the group consisting of a 5. The anthraquinone compound having the methyl group and an ethyl group. formula:

("J NH:

O-OH:CH:OGH|CH:--OCH:CH2OCHaOHrOH 6. The anthraquinone compound having the formula:

I t) N-O-o-(JHmHmHr-0-cmomom-o-omomom-on JOSEPH B. DICKEY. ANTHONY LORIA.

REFERENCES CITED Number Name Date The following references are of record in the 35 2357176 (I) Dlckey 1944 file of this patent: 2,359,381 Perkins et a1. Oct. 3, 1944 2,391,011 (II) Dickey et a1. Dec. 18, 1945 UNITED STATES PATENTS 2,455,077 Seymour et a1 July 13, 1948 Number Name Date 1,938,029 Kugel Dec. 5, 1933 40 FOREIGN PATENTS 2,326,047 McNally et a1. Aug. 3, 1943 Number Country Date 2,353,108 Wuertz et a1. July 4, 1944 306,963 Great Britain May 27, 1930 

1. THE ANTHRAQUINONE COMPOUNDS HAVING THE FORMULA: 